Metal-organic frameworks as porous proppants

ABSTRACT

Metal-organic frame-works (MOFs) and its compositions for use as proppants in a method of treating subterranean formations. A method comprising contacting the formation with a fluid composition comprising a metal-organic framework comprised of at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion.

BACKGROUND OF THE INVENTION

Hydrocarbon-producing wells are often stimulated by hydraulic fracturingtreatments. In hydraulic fracturing treatments, a viscous fracturingfluid, which also functions as a carrier fluid, is pumped into aproducing zone to be fractured at a rate and pressure such that one ormore fractures are formed in the zone. Particulate solids for proppingopen the fractures, commonly referred to in the art as “proppant,” aregenerally suspended in at least a portion of the fracturing fluid sothat the particulate solids are deposited in the fractures when thefracturing fluid reverts to a thin fluid to be returned to the surface.The proppant deposited in the fractures functions to prevent thefractures from fully closing and maintains conductive channels throughwhich produced hydrocarbons can flow.

After the fracturing fluid, which is the carrier fluid for the proppant,deposits the proppant in the fracture, the fracture closes on theproppant. Such partially closed fractures apply pressure on proppantparticles. For this purpose, the interstitial space between particlesshould be sufficiently large, yet possess the mechanical strength towithstand closure stresses to hold fractures open after the fracturingpressure is withdrawn. Thus, for instance, large mesh proppants exhibitgreater permeability than small mesh proppants at low closure stresses,but they will mechanically fail and thereby produce very fineparticulates (“fines”) at high closure pressures.

Modifications of proppant particles could be used advantageously toimprove their performance in hydraulic fracturing systems. First, if theproppant particles were less dense, a less viscous fracturing fluidcould be used, which would still convey the particles to the target areabut which would be easier to pump into the formation. Second, proppantsshould remain where they are placed throughout the lifetime of the wellafter they have been injected into a fracture line. If changes withinthe reservoir during well production force the proppants out ofposition, production equipment can be damaged, and the conductivity ofthe reservoir formation can be decreased as the reservoir pores areplugged by the displaced proppants. Third, the proppants in the systemshould be resistant to closure stress once they are placed in thefracture. Closure stresses can range from 1700 psi in certain shale gaswells, up to and exceeding 15,000 psi for deep, high temperature wells.Care must be taken that the proppants do not fail under this stress,lest they be crushed into fine particles that can migrate to undesirablelocations within the well, thereby affecting production.

Sand is a common proppant, though untreated sand is prone to significantfines generation. Alternative proppant materials include ceramics andsintered bauxite.

BRIEF DESCRIPTION OF THE FIGURES

In the drawings, which are not necessarily drawn to scale, like numeralsdescribe substantially similar components throughout the several views.Like numerals having different letter suffixes represent differentinstances of substantially similar components. The drawings illustrategenerally, by way of example, but not by way of limitation, variousembodiments discussed in the present document.

FIG. 1 illustrates a drilling assembly in accordance with variousembodiments.

FIG. 2 illustrates a system for delivering a composition to asubterranean formation in accordance with various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

In satisfying the needs and others described above, the presentinvention provides metal organic frameworks (MOF) for use as a newcategory of proppant in fracking operations, such as in hydrocarbonwells.

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part bythe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Definitions

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.The statement “about X to Y” has the same meaning as “about X to aboutY,” unless indicated otherwise. Likewise, the statement “about X, Y, orabout Z” has the same meaning as “about X, about Y, or about Z,” unlessindicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” has the same meaning as “A, B,or A and B.” In addition, it is to be understood that the phraseology orterminology employed herein, and not otherwise defined, is for thepurpose of description only and not of limitation. Any use of sectionheadings is intended to aid reading of the document and is not to beinterpreted as limiting; information that is relevant to a sectionheading may occur within or outside of that particular section.

In the methods of manufacturing described herein, the steps can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited. Furthermore, specified steps can be carried out concurrentlyunless explicit claim language recites that they be carried outseparately. For example, a claimed step of doing X and a claimed step ofdoing Y can be conducted simultaneously within a single operation, andthe resulting process will fall within the literal scope of the claimedprocess.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

As used herein, the term “drilling fluid” refers to fluids, slurries, ormuds used in drilling operations downhole, such as during the formationof the wellbore.

As used herein, the term “stimulation fluid” refers to fluids orslurries used downhole during stimulation activities of the well thatcan increase the production of a well, including perforation activities.In some examples, a stimulation fluid can include a fracturing fluid oran acidizing fluid.

As used herein, the term “clean-up fluid” refers to fluids or slurriesused downhole during clean-up activities of the well, such as anytreatment to remove material obstructing the flow of desired materialfrom the subterranean formation. In one example, a clean-up fluid can bean acidification treatment to remove material formed by one or moreperforation treatments. In another example, a clean-up fluid can be usedto remove a filter cake.

As used herein, the term “fracturing fluid” refers to fluids or slurriesused downhole during fracturing operations.

As used herein, the term “spotting fluid” refers to fluids or slurriesused downhole during spotting operations, and can be any fluid designedfor localized treatment of a downhole region. In one example, a spottingfluid can include a lost circulation material for treatment of aspecific section of the wellbore, such as to seal off fractures in thewellbore and prevent sag. In another example, a spotting fluid caninclude a water control material. In some examples, a spotting fluid canbe designed to free a stuck piece of drilling or extraction equipment,can reduce torque and drag with drilling lubricants, preventdifferential sticking, promote wellbore stability, and can help tocontrol mud weight.

As used herein, the term “completion fluid” refers to fluids or slurriesused downhole during the completion phase of a well, including cementingcompositions.

As used herein, the term “remedial treatment fluid” refers to fluids orslurries used downhole for remedial treatment of a well. Remedialtreatments can include treatments designed to increase or maintain theproduction rate of a well, such as stimulation or clean-up treatments.

As used herein, the term “abandonment fluid” refers to fluids orslurries used downhole during or preceding the abandonment phase of awell.

As used herein, the term “acidizing fluid” refers to fluids or slurriesused downhole during acidizing treatments. In one example, an acidizingfluid is used in a clean-up operation to remove material obstructing theflow of desired material, such as material formed during a perforationoperation. In some examples, an acidizing fluid can be used for damageremoval.

As used herein, the term “cementing fluid” refers to fluids or slurriesused during cementing operations of a well. For example, a cementingfluid can include an aqueous mixture including at least one of cementand cement kiln dust. In another example, a cementing fluid can includea curable resinous material such as a polymer that is in an at leastpartially uncured state.

As used herein, the term “water control material” refers to a solid orliquid material that interacts with aqueous material downhole, such thathydrophobic material can more easily travel to the surface and such thathydrophilic material (including water) can less easily travel to thesurface. A water control material can be used to treat a well to causethe proportion of water produced to decrease and to cause the proportionof hydrocarbons produced to increase, such as by selectively bindingtogether material between water-producing subterranean formations andthe wellbore while still allowing hydrocarbon-producing formations tomaintain output.

As used herein, the term “packing fluid” refers to fluids or slurriesthat can be placed in the annular region of a well between tubing andouter casing above a packer. In various examples, the packing fluid canprovide hydrostatic pressure in order to lower differential pressureacross the sealing element, lower differential pressure on the wellboreand casing to prevent collapse, and protect metals and elastomers fromcorrosion.

As used herein, the term “fluid” refers to liquids and gels, unlessotherwise indicated.

As used herein, the term “subterranean material” or “subterraneanformation” refers to any material under the surface of the earth,including under the surface of the bottom of the ocean. For example, asubterranean formation or material can be any section of a wellbore andany section of a subterranean petroleum- or water-producing formation orregion in fluid contact with the wellbore. Placing a material in asubterranean formation can include contacting the material with anysection of a wellbore or with any subterranean region in fluid contacttherewith. Subterranean materials can include any materials placed intothe wellbore such as cement, drill shafts, liners, tubing, or screens;placing a material in a subterranean formation can include contactingwith such subterranean materials. In some examples, a subterraneanformation or material can be any below-ground region that can produceliquid or gaseous petroleum materials, water, or any sectionbelow-ground in fluid contact therewith. For example, a subterraneanformation or material can be at least one of an area desired to befractured, a fracture or an area surrounding a fracture, and a flowpathway or an area surrounding a flow pathway, wherein a fracture or aflow pathway can be optionally fluidly connected to a subterraneanpetroleum- or water-producing region, directly or through one or morefractures or flow pathways.

As used herein, “treatment of a subterranean formation” can include anyactivity directed to extraction of water or petroleum materials from asubterranean petroleum-or water-producing formation or region, forexample, including drilling, stimulation, hydraulic fracturing,clean-up, acidizing, completion, cementing, remedial treatment,abandonment, and the like.

As used herein, a “flow pathway” downhole can include any suitablesubterranean flow pathway through which two subterranean locations arein fluid connection. The flow pathway can be sufficient for petroleum orwater to flow from one subterranean location to the wellbore orvice-versa. A flow pathway can include at least one of a hydraulicfracture, and a fluid connection across a screen, across gravel pack,across proppant, including across resin-bonded proppant or proppantdeposited in a fracture, and across sand. A flow pathway can include anatural subterranean passageway through which fluids can flow. In someembodiments, a flow pathway can be a water source and can include water.In some embodiments, a flow pathway can be a petroleum source and caninclude petroleum. In some embodiments, a flow pathway can be sufficientto divert from a wellbore, fracture, or flow pathway connected theretoat least one of water, a downhole fluid, or a produced hydrocarbon.

As used herein, a “carrier fluid” refers to any suitable fluid forsuspending, dissolving, mixing, or emulsifying with one or morematerials to form a composition. For example, the carrier fluid can beat least one of crude oil, dipropylene glycol methyl ether, dipropyleneglycol dimethyl ether, dipropylene glycol methyl ether, dipropyleneglycol dimethyl ether, dimethyl formamide, diethylene glycol methylether, ethylene glycol butyl ether, diethylene glycol butyl ether,butylglycidyl ether, propylene carbonate, D-limonene, a C₂-C₄₀ fattyacid C₁-C₁₀ alkyl ester (e.g., a fatty acid methyl ester),tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethylsulfoxide, dimethyl formamide, a petroleum distillation product offraction (e.g., diesel, kerosene, napthas, and the like) mineral oil, ahydrocarbon oil, a hydrocarbon including an aromatic carbon-carbon bond(e.g., benzene, toluene), a hydrocarbon including an alpha olefin,xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic,maleic or succinic acid, methanol, ethanol, propanol (iso- or normal-),butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g.,cyclohexanone, hexane), water, brine, produced water, flowback water,brackish water, and sea water. The fluid can form about 0.001 wt % toabout 99.999 wt % of a composition or a mixture including the same, orabout 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97,98, 99, 99.9, 99.99, or about 99.999 wt % or more.

The term “shaped body” as used herein refers to any solid body that hasat least a two-dimensional outer contour and extends to at least 0.2 mmin at least one direction in space. No other restrictions apply, i.e.,the body may take any conceivable shape and may extend in any directionby any length so long as it extends to at least 0.2 mm in one direction.

Metal-Organic Framework

Some embodiments of the invention provide for a fluid composition andmethods of its use, the composition comprising a metal-organic framework(“MOF”). The MOF is a bulk material, typically present as a crystallinemicroporous or mesoporous solid, and it comprises as basic or molecularunits a plurality of metal ions and organic ligands that are at leastbidentate, and the ligands are thereby capable of coordinating to themetal ions. MOFs generally exhibit high surface areas and arewell-defined, rigid structures amenable to chemical and physical tuningby choice of metal and/or ligand. Repeated in two or three dimensions,the coordination of ligands to metals forms a lattice having pores, andthe lattice thus constitutes the MOF structure.

Combinations of metal ions and ligands are very numerous and, hence,MOFs are versatile as to properties, size of pores, and applications.The invention contemplates in this regard the use of MOFs as proppantsbecause MOFs can be manufactured into differently shaped bodies, asdefined herein, they can be calcined, and they exhibit high mechanicalstrength while simultaneously maintaining porosity toward gases andliquids, even at high temperatures.

Suitable metals for use in the porous MOF of the invention are selectedfrom metal ions of main group elements and of the subgroup elements ofthe periodic table of the elements, namely of the groups Ia, Ia, IIIa,IVa to VIIIa and Ib to VIb. Thus, in some embodiments, the metal isselected from the group consisting of components, particular referenceis made to Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn,Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Gd, Eu, Tb, and combinationsthereof. Exemplary metals according to some embodiments include Zn, Cu,Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, and combinations thereof.

The MOF material according to some embodiments of the inventioncomprises metal ions of these metal elements. In principle, anyavailable ion of a given metal is contemplated for use in the invention.Examples of metal ions include Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺,Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺,Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os²⁺, Os²⁺, Co²⁺, Rh²⁺, Rh³⁺, Ir²⁺,Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺,Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺,As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sn⁺, Bi⁵⁺, Bi³⁺ and Bi⁺.

In principle any compound can be used as a ligand for this purpose andthat fulfills the foregoing requirements. More specifically, the ligandfeatures at least two centers that are capable coordinating to the metalions of a metal salt, particularly with the metals of the aforementionedgroups. In some embodiments, such centers in a ligand are selected fromthe group consisting of carboxylates, phosphonates, amines, azides,cyanides, squaryl groups, heteroatoms (e.g., N, O, and S), andcombinations thereof.

In one embodiment, the ligand is selected from the group consisting of amonocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, atetracarboxylic acid, and imidazole. Contemplated in this regard areions, salts and combinations of such ligands. Illustrative ligands foruse in the invention include formic acid, acetic acid, oxalic acid,propanoic acid, butanedioic acid, (E)-butenedioic acid,benzene-1,4-dicarboxylic acid, benzene-1,3-dicarboxylic acid,benzene-1,3,5-tricarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid,2-bromo-1,4-benzenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid,biphenyl-3,3′,5,5′-tetracarboxylic acid, biphenyl-3,4′,5-tricarboxylicacid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid,1,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa-2,4-dienedioic acid,1,4-naphthalenedicarboxylic acid, pyrene-2,7-dicarboxylic acid,4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid, aspartic acid, glutamicacid, adenine, 4,4′-bypiridine, pyrimidine, pyrazine,pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole,1H-benzimidazole, 2-methyl-1H-imidazole, ions, salts, and combinationsthereof.

Some embodiments contemplate specific combinations of metal and ligand.For instance, in one embodiment the metal is Zn, i.e., the metal ion isZn²⁺, and the ligand is benzene-1,4-dicarboxylic acid, i.e, present as adicarboxylate dianion coordinated to Zn²⁺. In another embodiment, metalis Cu, i.e., the metal ion is Cu²⁺, and the ligand isbenzene-1,3,5-tricarboxylic acid., i.e., the correspondingtricarboxylate trianion.

Exemplary MOFs include those described in U.S. Pat. No. 5,648,508,EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p.3-20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al.,Topics in Catalysis 9 (1999) p. 105-111, and B. Chen et al., Science 291(2001) p. 1021-23. Specific examples of MOFs also include those basedupon the following metal and ligand combinations:

-   -   Zn₄O(BTE)(BPDC), where BTE³⁻=4,4′,4″-[benzene-1,3,5-triyl-tris        (ethyne-2,1-diyl)]tribenzoate and        BPDC²⁻=biphenyl-4,4′-dicarboxylate (MOF-210),    -   Zn₄O(BBC)₂, where BBC³⁻=4,4′,4″-[benzene-1,3,5-triyl-tris        (benzene-4,1-diyl)]tribenzoate (MOF-200),    -   Zn₄O(BTB)₂, where BTB³⁻=1,3,5-benzenetribenzoate (MOF-177),    -   Zn₄O(BDC)₃, where BDC²⁻=1,4-benzenedicarboxylate (MOF-5),    -   Mn₃[(Mn₄Cl)₄(BTT)₈]₂, where        H₃BTT=benzene-1,3,5-tris(1H-tetrazole),    -   Cu₃(BTC)₂(H₂O)₃, where H₃BTC=1,3,5-benzenetricarboxylic acid,        and    -   Zr₆O₄(OH)₄(BDC) where BDC²⁻=1,4-benzenedicarboxylate (UiO-66).

One advantage of the invention resides in the fact that MOFs typicallyare crystalline solids exhibiting low density, thereby rendering themamenable to suspension in fluids for ease of delivery to subterraneanformations. Thus in some embodiments, the MOF has a dry density of about0.2 g/cm³ to about 0.8 g/cm³. Consistent with this physical property, asmentioned above, MOFs according to the invention are porous materials,wherein pore sizes are tunable by judicious selection of metal andligand. In one embodiment, the pore size of the MOF ranges from about0.2 nm to about 30 nm, from about 0.5 nm to about 20 nm, and from about0.7 nm to about 2 nm.

According to one embodiment of the invention, the MOF is present as ashaped body, as defined herein. The shaped body is a macroscopic shapethat the MOF assumes. Because different shapes are possible withmanufacturing techniques, a variety of shapes and sizes of MOFs can bedeployed for use a proppant. Hence, in one embodiment, the shaped bodyhas a shortest dimension of at least about 0.2 mm and a longestdimension of about 3 mm. Within these general guidelines, according toother embodiments, the shaped body is selected from the group consistingof a spherical body, a cylindrical body, a disk-shaped pellet, andcombinations thereof. An illustrative shaped body is a spherical pellet.

Method of treating a subterranean formation

One embodiment of the present invention is a method of treating asubterranean formation, comprising contacting the formation with thecomposition described herein. In some embodiments, the composition isused in well completion operations, such as primary proppant treatmentsfor immobilizing proppant particulates (e.g., hydraulic fracturing,gravel packing, and frac-packing), remedial proppant/gravel treatments,near-wellbore formation sand consolidation treatments for sand control,consolidating-while-drilling target intervals, andplugging-and-abandonment of wellbores in subterranean formations.

Per another embodiment, the method further includes placing thecomposition in a subterranean formation. The placing of the compositionin the subterranean formation can include contacting the composition andany suitable part of the subterranean formation, or contacting thecomposition and a subterranean material, such as any suitablesubterranean material. The subterranean formation can be any suitablesubterranean formation. In some examples, the placing of the compositionin the subterranean formation includes contacting the composition withor placing the composition in at least one of a fracture, at least apart of an area surrounding a fracture, a flow pathway, an areasurrounding a flow pathway, and an area desired to be fractured. Theplacing of the composition in the subterranean formation can be anysuitable placing and can include any suitable contacting between thesubterranean formation and the composition. The placing of thecomposition in the subterranean formation can include at least partiallydepositing the composition in a fracture, flow pathway, or areasurrounding the same.

In still another embodiment, the method further comprises hydraulicfracturing, such as a method of hydraulic fracturing to generate afracture or flow pathway. The placing of the composition in thesubterranean formation or the contacting of the subterranean formationand the hydraulic fracturing can occur at any time with respect to oneanother; for example, the hydraulic fracturing occurs before, during,and/or after the contacting or placing. In some embodiments, thecontacting or placing occurs during the hydraulic fracturing, such asduring any suitable stage of the hydraulic fracturing, such as during atleast one of a pre-pad stage (e.g., during injection of water with noproppant, and additionally optionally mid- to low-strength acid), a padstage (e.g., during injection of fluid only with no proppant, with someviscosifier, such as to begin to break into an area and initiatefractures to produce sufficient penetration and width to allowproppant-laden later stages to enter), or a slurry stage of thefracturing (e.g., viscous fluid with proppant). The method can includeperforming a stimulation treatment at least one of before, during, andafter placing the composition in the subterranean formation in thefracture, flow pathway, or area surrounding the same. The stimulationtreatment can be, for example, at least one of perforating, acidizing,injecting of cleaning fluids, propellant stimulation, and hydraulicfracturing. In some embodiments, the stimulation treatment at leastpartially generates a fracture or flow pathway where the composition isplaced or contacted, or the composition is placed or contacted to anarea surrounding the generated fracture or flow pathway.

In one embodiment, the fluid composition comprises a carrier fluid. Anysuitable proportion of the composition can be one or more downholefluids or one or more carrier fluids. In some embodiments about 0.001 wt% to about 99.999 wt % of the composition is a downhole fluid or carrierliquid, or about 0.1 wt % to about 80 wt %, or about 1 wt % to about 50wt %, or about 1 wt % or more of the composition, or about 2 wt %, 3, 4,5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95,96, 97, 98, 99, 99.9, or about 99.99 wt % or more.

In accordance with another embodiment, the concentration of MOF in thecomposition varies from about 0.01 wt % to about 30 wt %. In oneembodiment, the concentration is about 0.1 wt % to about 10 wt %.

Other Components

In some embodiments, the composition comprises one or more surfactants.The surfactant facilitates the coating of the MOF on a subterraneansurface causing the MOF composition to flow into fractures and/or flowchannels within the subterranean formation. The surfactant is anysuitable surfactant, such that the composition can be used as describedherein. The surfactant is present in any suitable proportion of thecomposition, such that the composition can be used as described herein.For example, about 0.000,1 wt % to about 20 wt % of the compositionconstitutes one or more surfactants, about 0.001 wt % to about 1 wt %,or about 0.000,1 wt % or less, or about 0.001 wt %, 0.005, 0.01, 0.02,0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 wt % ormore.

In some embodiments, the surfactant is at least one of a cationicsurfactant, an anionic surfactant, and a non-ionic surfactant. In someembodiments, the ionic groups of the surfactant can include counterions,such that the overall charge of the ionic groups is neutral, whereas inother embodiments, no counterion can be present for one or more ionicgroups, such that the overall charge of the one or more ionic groups isnot neutral.

In one embodiment, the surfactant is a non-ionic surfactant. Examples ofnon-ionic surfactants include polyoxyethylene alkyl ethers,polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers,polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters,polyoxyethylene sorbitan alkyl esters, polyethylene glycol,polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols,polyoxyalkylene glycol modified polysiloxane surfactants, and mixtures,copolymers or reaction products thereof. For example, the surfactant ispolyglycol-modified trimethylsilylated silicate surfactant. Furtherexamples of non-ionic surfactants include, but are not limited to,condensates of ethylene oxide with long chain fatty alcohols or fattyacids such as a (C₁₂₋₁₆)alcohol, condensates of ethylene oxide with anamine or an amide, condensation products of ethylene and propyleneoxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol amides,sucrose esters, fluoro-surfactants, fatty amine oxides, polyoxyalkylenealkyl ethers such as polyethylene glycol long chain alkyl ether,polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters,polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycolcopolymers and alkylpolysaccharides, polymeric surfactants such aspolyvinyl alcohol (PVA) and polyvinylmethylether. In some embodiments,the surfactant is a polyoxyethylene fatty alcohol or mixture ofpolyoxyethylene fatty alcohols. In other embodiments, the surfactant isan aqueous dispersion of a polyoxyethylene fatty alcohol or mixture ofpolyoxyethylene fatty alcohols. In some examples, suitable non-ionicsurfactants include at least one of an alkyl polyglycoside, a sorbitanester, a methyl glucoside ester, an amine ethoxylate, a diamineethoxylate, a polyglycerol ester, an alkyl ethoxylate, an alcohol thathas been polypropoxylated and/or polyethoxylated, any derivativethereof, or any combination thereof.

Examples of anionic surfactants include, but are not limited to, alkylsulphates such as lauryl sulphate, polymers such as acrylates/C₁₀₋₃₀alkyl acrylate crosspolymer alkylbenzenesulfonic acids and salts such ashexylbenzenesulfonic acid, octylbenzenesulfonic acid,decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,cetylbenzenesulfonic acid and myristylbenzenesulfonic acid; the sulphateesters of monoalkyl polyoxyethylene ethers; alkylnapthylsulfonic acid;alkali metal sulfoccinates, sulfonated glyceryl esters of fatty acidssuch as sulfonated monoglycerides of coconut oil acids, salts ofsulfonated monovalent alcohol esters, amides of amino sulfonic acids,sulfonated products of fatty acid nitriles, sulfonated aromatichydrocarbons, condensation products of naphthalene sulfonic acids withformaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkylsulphates, ester sulphates, and alkarylsulfonates. Anionic surfactantsinclude alkali metal soaps of higher fatty acids, alkylaryl sulfonatessuch as sodium dodecyl benzene sulfonate, long chain fatty alcoholsulfates, olefin sulfates and olefin sulfonates, sulfatedmonoglycerides, sulfated esters, sulfonated ethoxylated alcohols,sulfosuccinates, alkane sulfonates, phosphate esters, alkylisethionates, alkyl taurates, and alkyl sarcosinates.

Suitable cationic surfactants include at least one of an arginine methylester, an alkanolamine, an alkylenediamide, an alkyl ester sulfonate, analkyl ether sulfonate, an alkyl ether sulfate, an alkali metal alkylsulfate, an alkyl or alkylaryl sulfonate, a sulfosuccinate, an alkyl oralkylaryl disulfonate, an alkyl disulfate, an alcohol polypropoxylatedor polyethoxylated sulfates, a taurate, an amine oxide, an alkylamineoxide, an ethoxylated amide, an alkoxylated fatty acid, an alkoxylatedalcohol, an ethoxylated fatty amine, an ethoxylated alkyl amine, abetaine, a modified betaine, an alkylamidobetaine, a quaternary ammoniumcompound, any derivative thereof, and any combination thereof. Examplesof suitable cationic surfactants can include quaternary ammoniumhydroxides such as octyl trimethyl ammonium hydroxide, dodecyl trimethylammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyldimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammoniumhydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethylammonium hydroxide, tallow trimethyl ammonium hydroxide and cocotrimethyl ammonium hydroxide as well as corresponding salts of thesematerials, fatty amines and fatty acid amides and their derivatives,basic pyridinium compounds, and quaternary ammonium bases ofbenzimidazolines and poly(ethoxylated/propoxylated) amines.

In some embodiments, the surfactant is selected from Tergitol™ 15-s-3,Tergitol™ 15-s-40, sorbitan monooleate, polyglycol-modifiedtrimethsilylated silicate, polyglycol-modified siloxanes,polyglycol-modified silicas, ethoxylated quaternary ammonium saltsolutions, cetyltrimethylammonium chloride or bromide solutions, anethoxylated nonyl phenol phosphate ester, and a (C₁₂-C₂₂)alkylphosphonate. In some examples, the surfactant is a sulfonate methylester, a hydrolyzed keratin, a polyoxyethylene sorbitan monopalmitate, apolyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitanmonooleate, a linear alcohol alkoxylate, an alkyl ether sulfate,dodecylbenzene sulfonic acid, a linear nonyl-phenol, dioxane, ethyleneoxide, polyethylene glycol, an ethoxylated castor oil,dipalmitoyl-phosphatidylcholine, sodium 4-(1′heptylnonyl)benzenesulfonate, polyoxyethylene nonyl phenyl ether, sodiumdioctyl sulphosuccinate, tetraethyleneglycoldodecylether, sodiumoctlylbenzenesulfonate, sodium hexadecyl sulfate, sodium laurethsulfate, decylamine oxide, dodecylamine betaine, dodecylamine oxide,N,N,N-trimethyl-l-octadecammonium chloride, xylenesulfonate and saltsthereof (e.g., sodium xylene sulfonate), sodium dodecyl sulfate,cetyltrimethylammonium bromide, any derivative thereof, or anycombination thereof.

In other embodiments, the surfactant is one of alkylpropoxy-ethoxysulfonate, alkyl propoxy-ethoxysulfate,alkylaryl-propoxy-ethoxysulfonate, a mixture of an ammonium salt of analkyl ether sulfate, cocoamidopropyl betaine, cocoamidopropyldimethylamine oxide, an ethoxylated alcohol ether sulfate, an alkyl oralkene amidopropyl betaine, an alkyl or alkene dimethylamine oxide, analpha-olefinic sulfonate surfactant, any derivative thereof, and anycombination thereof. Suitable surfactants also include polymericsurfactants, block copolymer surfactants, di-block polymer surfactants,hydrophobically modified surfactants, fluoro-surfactants, andsurfactants containing a non-ionic spacer-arm central extension and anionic or nonionic polar group. In some examples, the non-ionicspacer-arm central extension is the result of at least one ofpolypropoxylation and polyethoxylation.

In various embodiments, the surfactant is at least one of a substitutedor unsubstituted (C₅-C₅₀)hydrocarbylsulfate salt, a substituted orunsubstituted (C₅-C₅₀)hydrocarbylsulfate (C₁-C₂₀)hydrocarbyl esterwherein the (C₁-C₂₀)hydrocarbyl is substituted or unsubstituted, and asubstituted or unsubstituted (C₅-C₅₀)hydrocarbylbisulfate. Thesurfactant is at least one of a (C₅-C₂₀)alkylsulfate salt, a(C₅-C₂₀)alkylsulfate (C₁-C₂₀)alkyl ester and a (C₅-C₂₀)alkylbisulfate.In various embodiments the surfactant is a (C₈-C₁₅)alkylsulfate salt,wherein the counterion is any suitable counterion, such as Na⁺, K⁺, Li⁺,H⁺, Zn⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Zn²⁺, or Al³⁺. In some embodiments, thesurfactant is a (C₈-C₁₅) alkylsulfate salt sodium salt. In someembodiments, the surfactant is sodium dodecyl sulfate.

In various embodiments, the surfactant is a(C₅-C₅₀)hydrocarbyltri((C₁-C₅₀) hydrocarbyl)ammonium salt, wherein each(C₅-C₅₀)hydrocarbyl is independently selected. The counterion can be anysuitable counterion, such as Na⁺, K⁺, Li⁺, H⁺, Zn⁺, NH₄ ⁺, Ca²⁺, Mg²⁺,Zn²⁺, or Al³⁺. Alternatively, the surfactant is a (C₅-C₅₀) alkyltri((C₁-C₂₀) alkyl)ammonium salt, wherein each (C₅-C₅₀)alkyl isindependently selected. For instance, the surfactant is a(C₁₀-C₃₀)alkyltri ((C₁-C₁₀)alkyl) ammonium halide salt, wherein each(C₁₀-C₃₀) alkyl is independently selected. An exemplary surfactant iscetyltrimethylammonium bromide.

In some embodiments, the composition further comprises include ahydrolyzable ester. The hydrolyzable ester is any suitable hydrolyzableester. For example, the hydrolyzable ester is a C₁-C₅ mono-, di-, tri-,or tetra-alkyl ester of a C₂-C₄₀ mono-, di-, tri-, or tetra-carboxylicacid. The hydrolyzable ester is one of dimethylglutarate,dimethyladipate, dimethylsuccinate, sorbitol, catechol,dimethylthiolate, methyl salicylate, dimethylsalicylate, andtert-butylhydroperoxide. Any suitable wt % of the composition or a curedproduct thereof is the hydrolyzable ester, such as about 0.01 wt % toabout 20 wt %, or about 0.1 wt % to about 5 wt %, or about 0.01 wt % orless, or about 0.1 wt %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, orabout 20 wt % or more.

In other embodiments, the composition comprises at least one tackifier.The tackifier can be any suitable wt % of the composition or curedproduct thereof, such as about 0.001 wt % to about 50 wt %, about 0.01wt % to about 30 wt %, or about 0.001 wt % or less, or about 0.01 wt %,0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or about 50 wt % ormore. The tackifier is any suitable material having tackiness. Forexample, the tackifier is an adhesive or a resin. The term “resin” asused herein refers to any of numerous physically similar polymerizedsynthetics or chemically modified natural resins including thermoplasticmaterials and thermosetting materials. In some embodiments, thetackifier is at least one of a shellac, a polyamide, a silyl-modifiedpolyamide, a polyester, a polycarbonate, a polycarbamate, a urethane, anatural resin, an epoxy-based resin, a furan-based resin, aphenolic-based resin, a urea-aldehyde resin, and a phenol/phenolformaldehyde/furfuryl alcohol resin.

In some embodiments, the tackifier is one of bisphenol A diglycidylether resin, butoxymethyl butyl glycidyl ether resin, bisphenolA-epichlorohydrin resin, and bisphenol F resin. In other embodiments,the tackifier is one of an acrylic acid polymer, an acrylic acid esterpolymer, an acrylic acid homopolymer, an acrylic acid ester homopolymer,poly(methyl acrylate), poly(butyl acrylate), poly(2-ethylhexylacrylate), an acrylic acid ester copolymer, a methacrylic acidderivative polymer, a methacrylic acid homopolymer, a methacrylic acidester homopolymer, poly(methyl methacrylate), poly(butyl methacrylate),poly(2-ethylhexyl methacrylate), an acrylamidomethylpropane sulfonatepolymer or copolymer or derivative thereof, and an acrylicacid/acrylamidomethylpropane sulfonate copolymer. In still otherembodiments, the tackifier is a trimer acid, a fatty acid, a fattyacid-derivative, maleic anhydride, acrylic acid, a polyester, apolycarbonate, a polycarbamate, an aldehyde, formaldehyde, a dialdehyde,glutaraldehyde, a hemiacetal, an aldehyde-releasing compound, a diacidhalide, a dihalide, a dichloride, a dibromide, a polyacid anhydride,citric acid, an epoxide, furfuraldehyde, an aldehyde condensate, asilyl-modified polyamide, and a condensation reaction product of apolyacid and a polyamine.

In some embodiments, the tackifier includes an amine-containing polymerand/or is hydrophobically-modified. In some embodiments, the tackifierincludes one of a polyamine (e.g., spermidine and spermine), a polyimine(e.g., poly(ethylene imine) and poly(propylene imine)), a polyamide,poly(2-(N,N-dimethylamino)ethyl methacrylate),poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole), anda copolymer including monomers of at least one of the foregoing andmonomers of at least one non-amine-containing polymer such as of atleast one of polyethylene, polypropylene, polyethylene oxide,polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate,and polymethacrylate. The hydrophobic modification is any suitablehydrophobic modification, such as at least one C₄-C₃₀ hydrocarbylincluding at least one of a straight chain, a branched chain, anunsaturated C-C bond, an aryl group, and any combination thereof.

One advantage of the MOF composition described herein is that drydensity of the MOF proppant is relatively low such the fluid compositiontypically can be of low viscosity for effective transportation of thecomposition to, and contacting it with a subterranean surface. In someembodiments where viscosity is modified, however, the compositionincludes one or more viscosifiers. The viscosifier is any suitableviscosifier. The viscosifier provides an increased viscosity of thecomposition before injection into the subterranean formation, at thetime of injection into the subterranean formation, during travel througha tubular disposed in a borehole, once the composition reaches aparticular subterranean location, or some period of time after thecomposition reaches a particular subterranean location. In someembodiments, the viscosifier can be about 0.000,1 wt % to about 10 wt %of the composition or a cured product thereof, about 0.004 wt % to about0.01 wt %, or about 0.000,1 wt % or less, 0.000,5 wt %, 0.001, 0.005,0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt % ormore.

The viscosifier includes at least one of a substituted or unsubstitutedpolysaccharide, and a substituted or unsubstituted polyalkene (e.g., apolyethylene, wherein the ethylene unit is substituted or unsubstituted,derived from the corresponding substituted or unsubstituted ethene),wherein the polysaccharide or polyalkene is crosslinked oruncrosslinked. Exemplary viscosifiers include a polymer including atleast one monomer selected from the group consisting of ethylene glycol,acrylamide, vinyl acetate, 2-acrylamidomethylpropane sulfonic acid orits salts, trimethylammoniumethyl acrylate halide, andtrimethylammoniumethyl methacrylate halide. The viscosifier can includea crosslinked gel or a crosslinkable gel. The viscosifier can include atleast one of a linear polysaccharide, and a poly((C₂-C₁₀)alkene),wherein the (C₂-C₁₀)alkene is substituted or unsubstituted. Theviscosifier can include at least one of poly(acrylic acid) or(C₁-C₅)alkyl esters thereof, poly(methacrylic acid) or (C₁-C₅)alkylesters thereof, poly(vinyl acetate), poly(vinyl alcohol), poly(ethyleneglycol), poly(vinyl pyrrolidone), polyacrylamide, poly (hydroxyethylmethacrylate), alginate, chitosan, curdlan, dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, welan, derivatized starch, tamarind, tragacanth, guar gum,derivatized guar (e.g., hydroxypropyl guar, carboxy methyl guar, orcarboxymethyl hydroxypropyl guar), gum ghatti, gum arabic, locust beangum, and derivatized cellulose (e.g., carboxymethyl cellulose,hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose,hydroxypropyl cellulose, or methyl hydroxy ethyl cellulose).

In some embodiments, the viscosifier is at least one of a poly(vinylalcohol) homopolymer, poly(vinyl alcohol) copolymer, a crosslinkedpoly(vinyl alcohol) homopolymer, and a crosslinked poly(vinyl alcohol)copolymer. The viscosifier can include a poly(vinyl alcohol) copolymeror a crosslinked poly(vinyl alcohol) copolymer including at least one ofa graft, linear, branched, block, and random copolymer of vinyl alcoholand at least one of a substituted or unsubstitued (C₂-C₅₀)hydrocarbylhaving at least one aliphatic unsaturated C-C bond therein, and asubstituted or unsubstituted (C₂-C₅₀)alkene. The viscosifier can includea poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol)copolymer including at least one of a graft, linear, branched, block,and random copolymer of vinyl alcohol and at least one of vinylphosphonic acid, vinylidene diphosphonic acid, substituted orunsubstituted 2-acrylamido-2-methylpropanesulfonic acid, a substitutedor unsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid,pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoicacid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid,acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid,vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid,crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid,allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and asubstituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate,vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, andvinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted(C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoicanhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substitutedor unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride,butenoic acid anhydride, pentenoic acid anhydride, hexenoic acidanhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoicacid anhydride, acrylic acid anhydride, fumaric acid anhydride,methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinylphosphonic acid anhydride, vinylidene diphosphonic acid anhydride,itaconic acid anhydride, crotonic acid anhydride, mesoconic acidanhydride, citraconic acid anhydride, styrene sulfonic acid anhydride,allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinylsulfonic acid anhydride, and an N-(C₁-C₁₀)alkenyl nitrogen containingsubstituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier caninclude a poly(vinyl alcohol) copolymer or a crosslinked poly(vinylalcohol) copolymer including at least one of a graft, linear, branched,block, and random copolymer that includes apoly(vinylalcohol/acrylamide) copolymer, apoly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid) copolymer,a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer,or a poly(vinylalcohol/N-vinylpyrrolidone) copolymer. The viscosifiercan include a crosslinked poly(vinyl alcohol) homopolymer or copolymerincluding a crosslinker including at least one of chromium, aluminum,antimony, zirconium, titanium, calcium, boron, iron, silicon, copper,zinc, magnesium, and an ion thereof. The viscosifier can include acrosslinked poly(vinyl alcohol) homopolymer or copolymer including acrosslinker including at least one of an aldehyde, an aldehyde-formingcompound, a carboxylic acid or an ester thereof, a sulfonic acid or anester thereof, a phosphonic acid or an ester thereof, an acid anhydride,and an epihalohydrin.

In some embodiments, the composition comprises one or more breakers. Thebreaker is any suitable breaker, such that the surrounding fluid (e.g.,a fracturing fluid) is at least partially broken for more complete andmore efficient recovery thereof, such as at the conclusion of thehydraulic fracturing treatment. In some embodiments, the breaker isencapsulated or otherwise formulated to give a delayed-release or atime-release breaker, such that the surrounding liquid remains viscousfor a suitable amount of time prior to breaking. The breaker is anysuitable breaker; such as a compound that includes a Na⁺, K⁺, Li⁺, Zn⁺,NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and an Al³⁺ salt of achloride, fluoride, bromide, phosphate, or sulfate ion. In someexamples, the breaker can be an oxidative breaker or an enzymaticbreaker. An oxidative breaker is at least one of a Na⁺, K⁺, Li⁺, Zn⁺,NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, , Ca²⁺, Mg²⁺, An²⁺, and an Al³⁺ salt of apersulfate, percarbonate, perborate, peroxide, perphosphosphate,permanganate, chlorite, or hyperchlorite ion. An enzymatic breaker is atleast one of an alpha or beta amylase, amyloglucosidase,oligoglucosidase, invertase, maltase, cellulase, hemi-cellulase, andmannanohydrolase. The breaker can be about 0.001 wt % to about 30 wt %of the composition, or about 0.01 wt % to about 5 wt %, or about 0.001wt % or less, or about 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5,6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more.

In accordance with one embodiment, the composition comprises anysuitable fluid in addition to those otherwise described herein. Forexample, the fluid is at least one of crude oil, dipropylene glycolmethyl ether, dipropylene glycol dimethyl ether, dipropylene glycolmethyl ether, dipropylene glycol dimethyl ether, dimethyl formamide,diethylene glycol methyl ether, ethylene glycol butyl ether, diethyleneglycol butyl ether, butylglycidyl ether, propylene carbonate,D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester (e.g., a fatty acidmethyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfurylacrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfurylacetate, dimethyl sulfoxide, dimethyl formamide, a petroleumdistillation product of fraction (e.g., diesel, kerosene, napthas, andthe like) mineral oil, a hydrocarbon oil, a hydrocarbon including anaromatic carbon-carbon bond (e.g., benzene, toluene), a hydrocarbonincluding an alpha olefin, xylenes, an ionic liquid, methyl ethylketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol,propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), analiphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine,produced water, flowback water, brackish water, and sea water. The fluidconstitutes about 0.001 wt % to about 99.999 wt % of the composition orabout 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97,98, 99, 99.9, 99.99, or about 99.999 wt % or more.

In other embodiments, the composition comprises a downhole fluid. Thecomposition can be combined with any suitable downhole fluid before,during, or after the placement of the composition in the subterraneanformation or the contacting of the composition and the subterraneanmaterial. In some examples, the composition is combined with a downholefluid above the surface, and then the combined composition is placed ina subterranean formation or contacted with a subterranean material. Inanother example, the composition is injected into a subterraneanformation to combine with a downhole fluid, and the combined compositionis contacted with a subterranean material or is considered to be placedin the subterranean formation.

In some embodiments, the downhole fluid is an aqueous or oil-based fluidincluding a fracturing fluid, spotting fluid, clean-up fluid, completionfluid, remedial treatment fluid, abandonment fluid, pill, cementingfluid, packer fluid, or a combination thereof. The placement of thecomposition in the subterranean formation can include contacting thesubterranean material and the mixture. The downhole fluid constitutesany suitable weight percent of the composition, such as about 0.001 wt %to about 99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt% to about 99.9 wt %, about 20 wt % to about 90 wt %, or about 0.001 wt% or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40,50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99wt %, or about 99.999 wt %.

In some embodiments, the composition includes an amount of any suitablematerial used in a downhole fluid. For example, the composition includeswater, saline, aqueous base, acid, oil, organic solvent, synthetic fluidoil phase, aqueous solution, alcohol or polyol, cellulose, starch,alkalinity control agents, acidity control agents, density controlagents, density modifiers, emulsifiers, dispersants, polymericstabilizers, crosslinking agents, polyacrylamide, a polymer orcombination of polymers, antioxidants, heat stabilizers, foam controlagents, solvents, diluents, plasticizer, filler or inorganic particle,pigment, dye, precipitating agent, rheology modifier, oil-wettingagents, set retarding additives, surfactants, gases, weight reducingadditives, heavy-weight additives, lost circulation materials,filtration control additives, salts, fibers, thixotropic additives,breakers, crosslinkers, rheology modifiers, curing accelerators, curingretarders, pH modifiers, chelating agents, scale inhibitors, enzymes,resins, water control materials, oxidizers, markers, Portland cement,pozzolana cement, gypsum cement, high alumina content cement, slagcement, silica cement, fly ash, metakaolin, shale, zeolite, acrystalline silica compound, amorphous silica, hydratable clays,microspheres, pozzolan lime, or a combination thereof.

In still other embodiments, the composition includes one or moreadditive components such as: thinner additives such as COLDTROL®, ATC®,OMC 2™, and OMC 42™; RHEMOD™, a viscosifier and suspension agentincluding a modified fatty acid; additives for providing temporaryincreased viscosity, such as for shipping (e.g., transport to the wellsite) and for use in sweeps (for example, additives having the tradename TEMPERUS™ (a modified fatty acid) and VIS-PLUS®, a thixotropicviscosifying polymer blend); TAU-MOD™, a viscosifying/suspension agentincluding an amorphous/fibrous material; additives for filtrationcontrol, for example, ADAPTA®, a high temperature high pressure (HTHP)filtration control agent including a crosslinked copolymer; DURATONE®HT, a filtration control agent that includes an organophilic lignite,more particularly organophilic leonardite; THERMO TONE™, a HTHPfiltration control agent including a synthetic polymer; BDF™-366, a HTHPfiltration control agent; BDF™-454, a HTHP filtration control agent;LIQUITONE™, a polymeric filtration agent and viscosifier; additives forHTHP emulsion stability, for example, FACTANT™, which includes highlyconcentrated tall oil derivative; emulsifiers such as LE SUPERMUL™ andEZ MUL® NT, polyaminated fatty acid emulsifiers, and FORTI-MUL®; DRILTREAT®, an oil wetting agent for heavy fluids; BARACARB®, a sized groundmarble bridging agent; BAROID®, a ground barium sulfate weighting agent;BAROLIFT®, a hole sweeping agent; SWEEP-WATE®, a sweep weighting agent;BDF-508, a diamine dimer rheology modifier; GELTONE® II organophilicclay; BAROFIBRE™ O for lost circulation management and seepage lossprevention, including a natural cellulose fiber; STEELSEAL®, a resilientgraphitic carbon lost circulation material; HYDRO-PLUG®, a hydratableswelling lost circulation material; lime, which can provide alkalinityand can activate certain emulsifiers; and calcium chloride, which canprovide salinity. Any suitable proportion of the composition can includeany optional component described hereinabove, such as about 0.001 wt %to about 99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt% to about 99.9 wt %, about 20 to about 90 wt %, or about 0.001 wt % orless, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50,60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt%, or about 99.999 wt % or more.

A cement fluid includes an aqueous mixture cement and/or cement kilndust. The composition including the aryl component and the amine orepoxide component, or a cured product thereof, can form a usefulcombination with cement or cement kiln dust. The cement kiln dust is anysuitable cement kiln dust. Cement kiln dust is formed during themanufacture of cement and can be partially calcined kiln feed that isremoved from the gas stream and collected in a dust collector during amanufacturing process. Cement kiln dust is advantageously utilized in acost-effective manner since kiln dust is often regarded as a low valuewaste product of the cement industry. Some embodiments of the cementfluid include cement kiln dust but no cement, cement kiln dust andcement, or cement but no cement kiln dust. The cement is any suitablecement. The cement can be a hydraulic cement, for instance. A variety ofcements can be utilized in accordance with embodiments of the presentinvention; for example, those including calcium, aluminum, silicon,oxygen, iron, or sulfur, which can set and harden by reaction withwater. Other suitable cements include Portland cements, pozzolanacements, gypsum cements, high alumina content cements, slag cements,silica cements, and combinations thereof. In some embodiments, thePortland cements that are suitable for use in embodiments of the presentinvention are classified as Classes A, C, H, and G cements according tothe American Petroleum Institute. A cement can be generally included inthe cementing fluid in an amount sufficient to provide the desiredcompressive strength, density, or cost. In some embodiments, thehydraulic cement can be present in the cementing fluid in an amount inthe range of from 0 wt % to about 100 wt %, about 0 wt % to about 95 wt%, about 20 wt % to about 95 wt %, or about 50 wt % to about 90 wt %. Acement kiln dust can be present in an amount of at least about 0.01 wt%, or about 5 wt % to about 80 wt %, or about 10 wt % to about 50 wt %.

Optionally, other additives are added to a cement or kilndust-containing composition of embodiments of the present invention asdeemed appropriate by one skilled in the art, with the benefit of thisdisclosure. For example, the composition can include fly ash,metakaolin, shale, zeolite, set retarding additive, surfactant, a gas,accelerators, weight reducing additives, heavy-weight additives, lostcirculation materials, filtration control additives, dispersants, andcombinations thereof. In some examples, additives include crystallinesilica compounds, amorphous silica, salts, fibers, hydratable clays,microspheres, pozzolan lime, thixotropic additives, and combinationsthereof.

In accordance with another embodiment, the composition described hereincomprises a binder. A binder is useful, for instance, in the formationof shaped bodies of the MOF composition, as described above. Forinstance, the binder is selected from the group consisting of hydratedaluminum-containing binders, titanium dioxide, hydrated titaniumdioxide, clay minerals, alkoxysilanes, amphiphilic substances, graphite,and combinations thereof. Further examples of suitable binders includehydrated alumina or other aluminum-containing binders, mixtures ofsilicon and aluminum compounds such as disclosed in WO 94/13584); andsilicon compounds.

Still further examples binders suitable for use in the invention includeoxides of silicon, aluminum, boron, phosphorus, zirconium, and/ortitanium. An illustrative binder, according to one embodiment, issilica, where the SiO₂ subunit is introduced into a shaping step as asilica sol or in the form of tetraalkoxysilanes, such in the formationof the shaped bodies described herein. Still further examples of bindersinclude oxides of magnesium and of beryllium and clays, such asmontmorillonites, kaolins, bentonites, halloysites, dickites, nacritesand anauxites. Tetraalkoxysilanes also are suitable for use as bindersin the present invention. Specific examples include tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane.Tetraalkoxytitanium and tetraalkoxyzirconium compounds and trimethoxy-,triethoxy-, tripropoxy- and tributoxy-aluminum, tetramethoxysilane andtetraethoxysilane are still further examples of suitable binders.

System

In accordance with an embodiment, the invention provides a system thatuses or that can be generated by use of an embodiment of the compositiondescribed herein in a subterranean formation, or that can perform or begenerated by performance of a method for using the composition describedherein. For instance, the system includes a composition and asubterranean formation including the composition therein. In someembodiments, the composition in the system includes a downhole fluid, orthe system comprises a mixture of the composition and downhole fluid. Inother embodiments, the system comprises a tubular and a pump configuredto pump the composition into the subterranean formation through thetubular.

Some embodiments provide a system configured for delivering thecomposition described herein to a subterranean location and for usingthe composition therein, such as for a fracturing operation (e.g.,pre-pad, pad, slurry, or finishing stages). In some embodiments, thesystem or apparatus includes a pump fluidly coupled to a tubular (e.g.,any suitable type of oilfield pipe, such as pipeline, drill pipe,production tubing, and the like), the tubular containing a compositionas described herein.

In some embodiments, the system comprises a drillstring disposed in awellbore, the drillstring including a drill bit at a downhole end of thedrillstring. The system can also include an annulus between thedrillstring and the wellbore. Further, in accordance with oneembodiment, the system includes a pump configured to circulate thecomposition through the drill string, through the drill bit, and backabove-surface through the annulus. In some embodiments, the systemincludes a fluid processing unit configured to process the compositionexiting the annulus to generate a cleaned drilling fluid forrecirculation through the wellbore.

The pump is a high pressure pump in some embodiments. As used herein,the term “high pressure pump” refers to a pump that is capable ofdelivering a fluid to a subterranean formation (e.g., downhole) at apressure of about 1000 psi or greater. A high pressure pump can be usedwhen it is desired to introduce the composition to a subterraneanformation at or above a fracture gradient of the subterranean formation,but it can also be used in cases where fracturing is not desired. Insome embodiments, the high pressure pump can be capable of fluidlyconveying particulate matter, such as proppant particulates, into thesubterranean formation. Suitable high pressure pumps are known to onehaving ordinary skill in the art and can include floating piston pumpsand positive displacement pumps.

In other embodiments, the pump is a low pressure pump. As used herein,the term “low pressure pump” refers to a pump that operates at apressure of about 1000 psi or less. In some embodiments, a low pressurepump can be fluidly coupled to a high pressure pump that is fluidlycoupled to the tubular. That is, in such embodiments, the low pressurepump is configured to convey the composition to the high pressure pump.In such embodiments, the low pressure pump can “step up” the pressure ofthe composition before it reaches the high pressure pump.

In some embodiments, the system described herein further includes amixing tank that is upstream of the pump and in which the composition isformulated. In various embodiments, the pump (e.g., a low pressure pump,a high pressure pump, or a combination thereof) conveys the compositionfrom the mixing tank or other source of the composition to the tubular.In other embodiments, however, the composition e formulated offsite andtransported to a worksite, in which case the composition is introducedto the tubular via the pump directly from its shipping container (e.g.,a truck, a railcar, a barge, or the like) or from a transport pipeline.In either case, the composition is drawn into the pump, elevated to anappropriate pressure, and then introduced into the tubular for deliveryto the subterranean formation.

With reference to FIG. 1, the composition directly or indirectly affectsone or more components or pieces of equipment associated with a wellboredrilling assembly 100, according to one or more embodiments. While FIG.1 generally depicts a land-based drilling assembly, those skilled in theart will readily recognize that the principles described herein areequally applicable to subsea drilling operations that employ floating orsea-based platforms and rigs, without departing from the scope of thedisclosure.

As illustrated, the drilling assembly 100 can include a drillingplatform 102 that supports a derrick 104 having a traveling block 106for raising and lowering a drill string 108. The drill string 108 mayinclude, but is not limited to, drill pipe and coiled tubing, asgenerally known to those skilled in the art. A kelly 110 supports thedrill string 108 as it is lowered through a rotary table 112. A drillbit 114 is attached to the distal end of the drill string 108 and isdriven either by a downhole motor and/or via rotation of the drillstring 108 from the well surface. As the bit 114 rotates, it creates awellbore 116 that penetrates various subterranean formations 118.

A pump 120 (e.g., a mud pump) circulates drilling fluid 122 through afeed pipe 124 and to the kelly 110, which conveys the drilling fluid 122downhole through the interior of the drill string 108 and through one ormore orifices in the drill bit 114. The drilling fluid 122 is thencirculated back to the surface via an annulus 126 defined between thedrill string 108 and the walls of the wellbore 116. At the surface, therecirculated or spent drilling fluid 122 exits the annulus 126 and maybe conveyed to one or more fluid processing unit(s) 128 via aninterconnecting flow line 130. After passing through the fluidprocessing unit(s) 128, a “cleaned” drilling fluid 122 is deposited intoa nearby retention pit 132 (e.g., a mud pit). While illustrated as beingarranged at the outlet of the wellbore 116 via the annulus 126, thoseskilled in the art will readily appreciate that the fluid processingunit(s) 128 may be arranged at any other location in the drillingassembly 100 to facilitate its proper function, without departing fromthe scope of the disclosure.

The composition may be added to, among other things, a drilling fluid122 via a mixing hopper 134 communicably coupled to or otherwise influid communication with the retention pit 132. The mixing hopper 134may include, but is not limited to, mixers and related mixing equipmentknown to those skilled in the art. In other embodiments, however, thecomposition is added to, among other things, a drilling fluid 122 at anyother location in the drilling assembly 100. In at least one embodiment,for example, there is more than one retention pit 132, such as multipleretention pits 132 in series. Moreover, the retention pit 132 canrepresent one or more fluid storage facilities and/or units where thecomposition may be stored, reconditioned, and/or regulated until addedto a drilling fluid 122.

As mentioned above, the composition may directly or indirectly affectthe components and equipment of the drilling assembly 100. For example,the composition may directly or indirectly affect the fluid processingunit(s) 128, which may include, but is not limited to, one or more of ashaker (e.g., shale shaker), a centrifuge, a hydrocyclone, a separator(including magnetic and electrical separators), a desilter, a desander,a separator, a filter (e.g., diatomaceous earth filters), a heatexchanger, or any fluid reclamation equipment. The fluid processingunit(s) 128 may further include one or more sensors, gauges, pumps,compressors, and the like used to store, monitor, regulate, and/orrecondition the composition.

The composition may directly or indirectly affect the pump 120, which isintended to represent one or more of any conduits, pipelines, trucks,tubulars, and/or pipes used to fluidically convey the compositiondownhole, any pumps, compressors, or motors (e.g., topside or downhole)used to drive the composition into motion, any valves or related jointsused to regulate the pressure or flow rate of the composition, and anysensors (e.g., pressure, temperature, flow rate, and the like), gauges,and/or combinations thereof, and the like. The composition may alsodirectly or indirectly affect the mixing hopper 134 and the retentionpit 132 and their assorted variations.

The composition can also directly or indirectly affect various downholeequipment and tools that comes into contact with the composition suchas, but not limited to, the drill string 108, any floats, drill collars,mud motors, downhole motors, and/or pumps associated with the drillstring 108, and any measurement while drilling (MWD)/logging whiledrilling (LWD) tools and related telemetry equipment, sensors, ordistributed sensors associated with the drill string 108. Thecomposition may also directly or indirectly affect any downhole heatexchangers, valves and corresponding actuation devices, tool seals,packers and other wellbore isolation devices or components, and the likeassociated with the wellbore 116.

While not specifically illustrated herein, the composition may alsodirectly or indirectly affect any transport or delivery equipment usedto convey the composition to the drilling assembly 100 such as, forexample, any transport vessels, conduits, pipelines, trucks, tubulars,and/or pipes used to fluidically move the composition from one locationto another, any pumps, compressors, or motors used to drive thecomposition into motion, any valves or related joints used to regulatethe pressure or flow rate of the composition, and any sensors (e.g.,pressure and temperature), gauges, and/or combinations thereof, and thelike.

FIG. 2 shows an illustrative schematic of systems that can deliverembodiments of the compositions of the present invention to asubterranean location, according to one or more embodiments. It shouldbe noted that while FIG. 2 generally depicts a land-based system orapparatus, like systems and apparatuses can be operated in subsealocations as well. Embodiments of the present invention can have adifferent scale than that depicted in FIG. 2. As depicted in FIG. 2,system or apparatus 1 can include mixing tank 10, in which an embodimentof the composition can be formulated. The composition can be conveyedvia line 12 to wellhead 14, where the composition enters tubular 16,with tubular 16 extending from wellhead 14 into subterranean formation18. Upon being ejected from tubular 16, the composition can subsequentlypenetrate into subterranean formation 18. Pump 20 can be configured toraise the pressure of the composition to a desired degree before itsintroduction into tubular 16. It is to be recognized that system orapparatus 1 is merely exemplary in nature and various additionalcomponents can be present that have not necessarily been depicted inFIG. 2 in the interest of clarity. In some examples, additionalcomponents that can be present include supply hoppers, valves,condensers, adapters, joints, gauges, sensors, compressors, pressurecontrollers, pressure sensors, flow rate controllers, flow rate sensors,temperature sensors, and the like.

Although not depicted in FIG. 2, at least part of the composition can,in some embodiments, flow back to wellhead 14 and exit subterraneanformation 18. The composition that flows back can be substantiallydiminished in the concentration of various components therein. In someembodiments, the composition that has flowed back to wellhead 14 cansubsequently be recovered, and in some examples reformulated, andrecirculated to subterranean formation 18.

The composition of the invention can also directly or indirectly affectthe various downhole or subterranean equipment and tools that can comeinto contact with the composition during operation. Such equipment andtools can include wellbore casing, wellbore liner, completion string,insert strings, drill string, coiled tubing, slickline, wireline, drillpipe, drill collars, mud motors, downhole motors and/or pumps,surface-mounted motors and/or pumps, centralizers, turbolizers,scratchers, floats (e.g., shoes, collars, valves, and the like), loggingtools and related telemetry equipment, actuators (e.g.,electromechanical devices, hydromechanical devices, and the like),sliding sleeves, production sleeves, plugs, screens, filters, flowcontrol devices (e.g., inflow control devices, autonomous inflow controldevices, outflow control devices, and the like), couplings (e.g.,electro-hydraulic wet connect, dry connect, inductive coupler, and thelike), control lines (e.g., electrical, fiber optic, hydraulic, and thelike), surveillance lines, drill bits and reamers, sensors ordistributed sensors, downhole heat exchangers, valves and correspondingactuation devices, tool seals, packers, cement plugs, bridge plugs, andother wellbore isolation devices or components, and the like. Any ofthese components can be included in the systems and apparatusesgenerally described above and depicted in FIG. 2.

Additional Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 is a method of treating a subterranean formation, themethod comprising contacting the formation with a fluid compositioncomprising a metal-organic framework comprised of at least one metal ionand an organic ligand that is at least bidentate and that is bonded tothe metal ion.

Embodiment 2 relates to embodiment 1, wherein the metal ion is selectedfrom available ions of base elements in the group consisting of Mg, Ca,Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co,Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn,Pb, As, Sb, Bi, Gd, Eu, Tb, and combinations thereof.

Embodiment 3 relates to embodiment 2, wherein the base element isselected from the group consisting of Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd,Mg, Ca, Zr, and combinations thereof.

Embodiment 4 relates to any of embodiments 1-3, wherein the ligandcontains at least one functional group selected from the groupconsisting of a carboxylate, a phosphonate, an amine, an azide, acyanide, a squaryl, an heteroatom, and combinations thereof.

Embodiment 5 relates to any of embodiments 1-4, wherein the ligand isselected from the group consisting of a monocarboxylic acid, adicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid,imidazole, ions, salts and combinations thereof.

Embodiment 6 relates to any of embodiments 1-5, wherein the ligand isselected from the group consisting of formic acid, acetic acid, oxalicacid, propanoic acid, butanedioic acid, (E)-butenedioic acid,benzene-1,4-dicarboxylic acid, benzene-1,3-dicarboxylic acid,benzene-1,3,5-tricarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid,2-bromo-1,4-benzenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid,biphenyl-3,3′,5,5?-tetracarboxylic acid, biphenyl-3,4′,5-tricarboxylicacid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid,1,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa-2,4-dienedioic acid,1,4-naphthalenedicarboxylic acid, pyrene-2,7-dicarboxylic acid,4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid, aspartic acid, glutamicacid, adenine, 4,4′-bypiridine, pyrimidine, pyrazine,pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole,1H-benzimidazole, 2-methyl-1H-imidazole, ions, salts, and combinationsthereof.

Embodiment 7 relates to any of embodiments 1-6, wherein the metal ion isan ion of Zn and the ligand is benzene-1,4-dicarboxylic acid.

Embodiment 8 relates to any of embodiments 1-7, wherein the metal ion isan ion of Cu and the ligand is benzene-1,3,5-tricarboxylic acid.

Embodiment 9 relates to any of embodiments 1-8, wherein themetal-organic framework has a dry density of about 0.2 g/cm³ to about0.8 g/cm³.

Embodiment 10 relates to any of embodiments 1-9, wherein themetal-organic framework has a pore size from about 0.2 nm to about 30nm.

Embodiment 11 relates to any of embodiments 1-10, wherein themetal-organic framework is present in the form of a shaped body having ashortest dimension of at least about 0.2 mm and a longest dimension ofabout 3 mm.

Embodiment 12 relates to 11, wherein the shaped body is selected fromthe group consisting of a spherical body, a cylindrical body, adisk-shaped pellet, and combinations thereof.

Embodiment 13 relates to any of embodiments 1-12, wherein thecomposition further comprises a binder.

Embodiment 14 relates to embodiment 13, wherein the binder is selectedfrom the group consisting of hydrated aluminum-containing binders,titanium dioxide, hydrated titanium dioxide, clay minerals,alkoxysilanes, amphiphilic substances, graphite, and combinationsthereof.

Embodiment 15 relates to any of embodiments 1-14, wherein the contactingcomprises placing the composition in at least one of a fracture andflowpath in the subterranean formation.

Embodiment 16 relates embodiment 15, wherein the fracture is present inthe subterranean formation at the time when the composition is contactedwith the subterranean formation.

Embodiment 17 relates to any of embodiment 16, wherein the methodfurther comprises forming the fracture or flowpath.

Embodiment 18 relates to any of embodiments 1-17, wherein the contactingcomprises gravel packing.

Embodiment 19 relates to any of embodiments 1-18, further comprisingfracturing the subterranean formation to form at least one fracture inthe subterranean formation.

Embodiment 20 relates to any of embodiments 1-19, wherein thecomposition further comprises a carrier fluid.

Embodiment 21 relates to any of embodiments 1-20, wherein themetal-organic framework is present in an amount of about 0.01 wt % toabout 30 wt % based upon the total weight of the composition.

Embodiment 22 relates to any of embodiments 1-21, wherein themetal-organic framework is present in an amount of about 0.1 wt % toabout 10 wt %.

Embodiment 23 relates to any of embodiments 1-22, further comprisingcombining the composition with an aqueous or oil-based fluid comprisinga fracturing fluid, spotting fluid, clean-up fluid, completion fluid,remedial treatment fluid, abandonment fluid, pill, cementing fluid,packer fluid, or a combination thereof

Embodiment 24 is a system for performing the method of any ofembodiments 1-23, the system comprising a tubular disposed in thesubterranean formation; and a pump configured to pump the composition inthe subterranean formation through the tubular.

Embodiment 25 is a system comprising a fluid composition comprising ametal-organic framework comprised of at least one metal ion and anorganic ligand that is at least bidentate and that is bonded to themetal ion subterranean formation comprising the composition therein.

Embodiment 26 relates to embodiment 25, further comprising a tubulardisposed in the subterranean formation and a pump configured to pump thecomposition in the subterranean formation through the tubular.

We claim:
 1. A method of treating a subterranean formation the methodcomprising: contacting the formation with a fluid composition, the fluidcomposition comprises 0.01 to about 30 wt % based on the total weight ofthe fluid composition, of a proppant consisting essentially of ametal-organic framework, wherein the metal-organic framework consists ofa metal ion and an organic ligand, wherein the organic ligand is atleast bidentate and is bonded to the metal ion.
 2. The method accordingto claim 1, wherein the metal ion is selected from the group consistingof Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe,Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl,Si, Ge, Sn, Pb, As, Sb, Bi, Gd, Eu, Tb, and combinations thereof.
 3. Themethod according to claim 2, wherein the metal ion is selected from thegroup consisting of Zn, Cu, Ni, Co, Fe, Mn, Cr, Cd, Mg, Ca, Zr, andcombinations thereof.
 4. The method according to claim 1, wherein theligand contains a functional group selected from the group consisting ofa carboxylate, a phosphonate, an amine, an azide, a cyanide, a squaryl,a heteroatom, and combinations thereof.
 5. The method according to claim4, wherein (a) the ligand contains the carboxylate functional group andis selected from the group consisting of a monocarboxylic acid; adicarboxylic acid; a tricarboxylic acid; a tetracarboxylic acid; ions,salts and combinations thereof or (b) the ligand contains the heteroatomfunctional group and is selected from the group consisting of imidazole,ions, salts and combinations thereof.
 6. The method according to claim4, wherein (a) the ligand contains the carboxylate functional group andis selected from the group consisting of formic acid; acetic acid;oxalic acid; propanoic acid; butanedioic acid; (E)-butenedioic acid;benzene-1,4-dicarboxylic acid; benzene-1, 3-dicarboxylic acid;benzene-1,3,5-tricarboxylic acid; 2-amino-1,4-benzenedicarboxylic acid;2-bromo-1, 4-benzenedicarboxylic acid; biphenyl-4,4′-dicarboxylic acid;biphenyl-3,3′,5,5′-tetracarboxylic acid; biphenyl-3,4′,5- tricarboxylicacid; 2,5-dihydroxy-1,4-benzenedicarboxylic acid;1,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa-2,4-dienedioic acid;1,4-naphthalenedicarboxylic acid; pyrene-2,7-dicarboxylic acid;4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid; aspartic acid; glutamicacid; ions, salts, and combinations thereof or (b) the ligand containsthe heteroatom functional group and is selected from the groupconsisting of adenine; 4,4′- bypiridine; pyrimidine; pyrazine;pyridine-4-carboxylic acid; pyridine-3-carboxylic acid; imidazole;1H-benzimidazole; 2-methyl-1H-imidazole; ions, salts, and combinationsthereof.
 7. The method according to claim 1, wherein the metal ion is anion of Zn and the ligand is benzene-1,4-dicarboxylic acid.
 8. The methodaccording to claim 1, wherein the metal ion is an ion of Cu and theligand is benzene-1,3,5-tricarboxylic acid.
 9. The method according toclaim 1, wherein the metal-organic framework has a dry density of about0.2 g/cm³ to about 0.8 g/cm³.
 10. The method according to claim 1,wherein the metal-organic framework has a pore size from about 0.2 nm toabout 30 nm.
 11. The method according to claim 1, wherein themetal-organic framework is present in the form of a shaped body having afirst dimension of at least about 0.2 mm and a second dimension of about3 mm.
 12. The method according to claim 11, wherein the shaped body isselected from the group consisting of a spherical body, a cylindricalbody, a disk-shaped pellet, and combinations thereof.
 13. The methodaccording to claim 1, wherein the composition further comprises abinder.
 14. The method according to claim 13, wherein the binder isselected from the group consisting of hydrated aluminum-containingbinders, titanium dioxide, hydrated titanium dioxide, clay minerals,alkoxysilanes, amphiphilic substances, graphite, and combinationsthereof.
 15. The method according to claim 1, wherein the contactingcomprises placing the composition in at least one of a fracture andflowpath in the subterranean formation.
 16. The method according toclaim 15, wherein the contacting comprises placing the composition in afracture, and wherein the fracture is present in the subterraneanformation when the composition is contacted with the subterraneanformation.
 17. The method according to claim 16, wherein the methodfurther comprises forming the fracture or flowpath.
 18. The methodaccording to claim 1, wherein the contacting comprises gravel packing.19. The method according to claim 1, further comprising fracturing thesubterranean formation to form at least one fracture in the subterraneanformation.
 20. The method according to claim 1, wherein the compositionfurther comprises a carrier fluid.
 21. The method according to claim 1,wherein the proppant is present in an amount of about 0.01 wt % to about20 wt % based upon the total weight of the composition.
 22. The methodaccording to claim 21, wherein the proppant is present in an amount ofabout 0.1 wt % to about 10 wt % based upon the total weight of thecomposition.
 23. The method according to claim 1, further comprisingcombining the composition with an aqueous or oil-based fluid comprisinga fracturing fluid, spotting fluid, clean-up fluid, completion fluid,remedial treatment fluid, abandonment fluid, pill, cementing fluid,packer fluid, or a combination thereof.
 24. A system for performing themethod of claim 1, the system comprising: a tubular disposed in thesubterranean formation; and a pump configured to pump the composition inthe subterranean formation through the tubular.
 25. A system comprising:a fluid composition, wherein the fluid composition comprises 0.01 toabout 30 wt. %, based on the total weight of the fluid composition, of aproppant consisting essentially of a metal-organic framework, whereinthe metal-organic framework consists of a metal ion and an organicligand, wherein the organic ligand is at least bidentate and is bondedto the metal ion; and subterranean formation comprising the compositiontherein.
 26. The system according to claim 25, further comprising: atubular disposed in the subterranean formation; a pump configured topump the composition in the subterranean formation through the tubular.